EP0180809B1 - Production of epoxy phosphates - Google Patents

Production of epoxy phosphates Download PDF

Info

Publication number
EP0180809B1
EP0180809B1 EP85112953A EP85112953A EP0180809B1 EP 0180809 B1 EP0180809 B1 EP 0180809B1 EP 85112953 A EP85112953 A EP 85112953A EP 85112953 A EP85112953 A EP 85112953A EP 0180809 B1 EP0180809 B1 EP 0180809B1
Authority
EP
European Patent Office
Prior art keywords
water
polyepoxide
epoxy
recited
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85112953A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0180809A1 (en
Inventor
Kazys Sekmakas
Raj Shah
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valspar Corp
Original Assignee
DeSoto Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DeSoto Inc filed Critical DeSoto Inc
Publication of EP0180809A1 publication Critical patent/EP0180809A1/en
Application granted granted Critical
Publication of EP0180809B1 publication Critical patent/EP0180809B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1427—Polycondensates modified by chemical after-treatment with inorganic compounds with water, e.g. hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines

Definitions

  • This invention relates to the production of epoxy phosphates having improved properties by a simplified process, and includes the resulting product.
  • Epoxy phosphates are known and have many uses in polymer chemistry.
  • the provision of epoxy phosphates which can be stably dispersed in aqueous medium has represented a difficult problem, as illustrated in U.S.-A- No. 4,397,970 in which resort is had to reacting the resinous polyepoxide with a phosphorous oxide or a mixture thereof with a limited amount of water insufficient to hydrate the phosphorous oxide to orthophosphoric acid.
  • the reaction product is subsequently hydrolyzed by reaction with water.
  • an excessive proportion of phosphorous is needed, the reaction procedure is difficult, and the product includes high molecular weight material which increases the viscosity in aqueous solution or dispersion.
  • US--A-40 59 550 discloses an adduct of phosphoric acid with an epoxy resin, but too much phosphoric acid and too little water is used, i.e. only that amount of water which is carried in by the 85% phosphoric acid, and this is inadequate. Also, one mole of phosphoric acid is used per equivalent of epoxide.
  • DE-A-30 09 715 describes similar adducts but, in the reaction, not all the epoxide groups which are present are consumed. As a result, much of the epoxy or oxirane functionality must have been consumed in side reactions, such as epoxide-epoxide reactions. Also, the temperature of reaction is usually about 50°C which is far too low such that reactoin of the oxirane groups with phosphoric acid and hydrolysis will not occur simultaneously.
  • EP-A-0 032 554 uses epoxy phosphates, but the proportions of total reactant is inadequate, the phosphoric acid is used in admixture with a phosphonic acid, and the reaction temperature is again inadequate to provoke the simultaneous reaction with the phosphoric acid and the hydrolysis of the oxirane group.
  • a process of producing a water dispersible epoxy phosphate-solvent mixture comprising heating said solvent with orthophosphoric acid (which contains water) to a reaction temperature sufficiently high to cause reaction with phosphoric acid and hydrolysis of the oxirane groups to occur simultaneously together with an amount of water such that the total amount of water is sufficient to hydrolyze at least 50% of the oxirane functionality in the polyepoxide which is used, slowly adding a resinous polyepoxide to said heated mixture so that the concentration of oxirane functionality in the reaction mixture will be minimized as the reaction proceeds, thus minimizing epoxy-epoxy reactions which increase the molecular weight of the epoxy phosphate which is formed, said phosphoric acid being used in an amount to provide from about 0.03 to about 0.9 moles of acid per equivalent of oxirane functionality in said polyepoxide, and then adding volatile amine to destroy any remaining oxirane functionality and to partially or fully neutralize the epoxy phosphate to provide a water dispersible epoxy phosphate
  • the proportion of water can be increased above the minimum specified above and may far exceed the equivalents of polyepoxide, as illustrated in Example 1 hereinafter.
  • the amount of water is preferably at least 75% of the oxirane functionality in the epxoy resin reactant.
  • reaction temperature will vary with the availability of pressure, but it is preferred to use a relatively high boiling solvent, like 2-butoxyethanol, and to use temperatures near the boiling point of water, e.g., 100° to 105°C.
  • a relatively high boiling solvent like 2-butoxyethanol
  • This invention also provides epoxy esters which, in coating compositions comprising an aminoplast or phenoplast curing agent, cure to provide improved adhesion and improved physical toughness (evidenced by superior abrasion resistance).
  • this invention provides products which are better because they provide superior coating compositions.
  • the proportion of orthophosphoric acid is preferably sufficient to provide from about 0.05 to about 0.3 moles of this acid per oxirane equivalent in the polyepoxide.
  • the presence of the phosphoric acid provides acidity which can be neutralized for salt formation, these salt groups enhancing dispersion in water.
  • the neutralizing volatile amine which is conventional and includes ammonia
  • the phosphoric acid groups catalyze the cure, especially with aminoplast resin.
  • the amount of phosphoric acid used is adjusted to provide the desired water dispersibility and cure enhancement, and these factors will vary with the polyepoxide selected, the proportion of solvent and the cure which is desired.
  • the resinous polyepoxides used herein may be constituted by any resinous polyepoxide having a 1,2-epoxy equivalency in excess of 1.2, but preferably from 1.4 to 2.0.
  • Diglycidyl ethers of bisphenol, such as bisphenol A, having an average molecular weight in the range of 350-7000 are preferred. Products of this type of both high and low molecular weights are illustrated in the examples.
  • aminoplast and phenoplast resins which can be used herein are well known, and any of these which are used in aqueous coating compositions are useful herein. Hexamethoxymethyl melamine is preferred herein, as illustrated in the examples.
  • the orthophosphoric acid reacts with some of the oxirane groups in the diglycidyl ether, and many of the oxirane groups are hydrolyzed as the reaction proceeds, thus minimizing the proportion of unreacted oxirane groups in the reactor.
  • the reaction mixture is maintained at 105°C. for 2 hours to insure completion of the esterification and hydrolysis reactions, and then the reaction mixture is cooled to 80°C.
  • This dispersion is equivalent to the product which can be produced using the process of U.S.-A-4,425,451 in which the same ratio of 914 parts of Epon 10070 to 24 parts of 85% orthophosphoric acid is used, but in the prior process it was necessary to heat the Epon 1007 9 to 125°C. and to hold it there for a long time while it dissolved in the 2-butoxy ethanol. Moreover, it took a total of 540 parts of 2-butoxyethanol to handle the 914 parts of Epon 1007 @ , while only 355 parts of 2-butoxyethanol are required in this example.
  • Example 1 can-be used in place of the epoxy phosphate described in U.S.-A-4,461,857 Example 5 to produce corresponding results in Examples 4 and 6 of that patent, superior adhesion and abrasion resistance being obtained.
  • Example 2 The product of Example 2 is also useful in the combinations disclosed in U.S.-A-4,425,451, but it is particularly useful for the coating of aluminum foil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
EP85112953A 1984-10-18 1985-10-12 Production of epoxy phosphates Expired EP0180809B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/662,162 US4598109A (en) 1984-10-18 1984-10-18 Production of epoxy phosphates
US662162 1984-10-18

Publications (2)

Publication Number Publication Date
EP0180809A1 EP0180809A1 (en) 1986-05-14
EP0180809B1 true EP0180809B1 (en) 1989-02-15

Family

ID=24656623

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85112953A Expired EP0180809B1 (en) 1984-10-18 1985-10-12 Production of epoxy phosphates

Country Status (7)

Country Link
US (1) US4598109A (enrdf_load_stackoverflow)
EP (1) EP0180809B1 (enrdf_load_stackoverflow)
JP (1) JPS6198724A (enrdf_load_stackoverflow)
AU (1) AU569575B2 (enrdf_load_stackoverflow)
CA (1) CA1255321A (enrdf_load_stackoverflow)
DE (1) DE3568277D1 (enrdf_load_stackoverflow)
MX (1) MX159981A (enrdf_load_stackoverflow)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171784A (en) * 1984-08-02 1992-12-15 Union Carbide Chemicals & Plastics Technology Corporation Phosphorylated reaction products and compositions incorporating such products
US4692484A (en) * 1985-09-25 1987-09-08 Desoto, Inc. Epoxy-phosphate/phenolic electrocoating compositions
US4957952A (en) * 1986-04-03 1990-09-18 Desoto, Inc. Anionic electrocoat compositions containing epoxy phosphates
US4737529A (en) * 1986-04-03 1988-04-12 Desoto, Inc. Cathodic electrocoat compositions containing epoxy phosphates
JPH0668094B2 (ja) * 1986-10-29 1994-08-31 旭電化工業株式会社 被覆用樹脂組成物
EP0275945A3 (en) * 1987-01-21 1989-11-08 DeSoto, Inc. Polyester coatings from terephthalate polyester plastics
US4847314A (en) * 1987-01-21 1989-07-11 Desoto, Inc. Polyester coatings from terephthalate polyester and hydroxy-functional linear polyester
US5001173A (en) * 1987-05-11 1991-03-19 Morton Coatings, Inc. Aqueous epoxy resin compositions and metal substrates coated therewith
US5082698A (en) * 1987-05-11 1992-01-21 Morton Coatings, Inc. Aqueous epoxy resin compositions and metal substrates coated therewith
US4801628A (en) * 1987-11-20 1989-01-31 Basf Corporation, Coatings And Inks Division Etherified phosphoric acid ester of epoxy resin
US4983654A (en) * 1987-12-28 1991-01-08 Ford Motor Company Phosphate/epoxy stabilizer for extrudable polyester blends
US5527840B1 (en) * 1994-10-04 1999-08-10 Valspar Corp Aqueous coating composition
US8148451B2 (en) * 2007-02-20 2012-04-03 Fenn William V Production of stable water dispersion epoxy phosphate ester resins and their aqueous coating compositions
CA2822750C (en) 2010-12-29 2019-11-12 Akzo Nobel Coatings International B.V. Adhesion promoter resin compositions and coating compositions having the adhesion promoter resin compositions
CN112358602A (zh) * 2020-10-21 2021-02-12 上海广沣科技有限公司 一种环氧磷酸酯树脂及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059550A (en) * 1976-07-06 1977-11-22 Celanese Polymer Specialties Company Aqueous dispersions of polyhydroxy polyether resins and aminoplast resins
AT367786B (de) * 1979-04-03 1982-07-26 Vianova Kunstharz Ag Verwendung von modifizierten epoxidharzen als bindemittel fuer grundfueller
DE3062301D1 (en) * 1979-12-24 1983-04-14 Vianova Kunstharz Ag Combination of binding agents for corrosion-proof lacquers
US4397970A (en) * 1981-06-24 1983-08-09 The Dow Chemical Company Process for epoxy phosphate coating resins
US4461857A (en) * 1982-09-29 1984-07-24 Desoto, Inc. Thermosetting aqueous coating compositions containing epoxy-phosphate dispersions
US4425451A (en) * 1982-09-29 1984-01-10 Desoto, Inc. Epoxy-phosphate aqueous dispersions

Also Published As

Publication number Publication date
JPH0519566B2 (enrdf_load_stackoverflow) 1993-03-17
JPS6198724A (ja) 1986-05-17
US4598109A (en) 1986-07-01
DE3568277D1 (en) 1989-03-23
EP0180809A1 (en) 1986-05-14
AU4819185A (en) 1986-04-24
MX159981A (es) 1989-10-18
CA1255321A (en) 1989-06-06
AU569575B2 (en) 1988-02-04

Similar Documents

Publication Publication Date Title
EP0180809B1 (en) Production of epoxy phosphates
US4425451A (en) Epoxy-phosphate aqueous dispersions
EP0082196B1 (en) Process for preparing epoxy resin/phosphoric acid reaction products
US5389704A (en) Epoxy phosphate ester resin, its production and coating composition containing the resin
AU599681B2 (en) Cationic, advanced epoxy resin composition
US4230552A (en) Novel pigment grinding vehicle
US3632836A (en) Solid curable polyepoxides modified with hydrolyzed liquid polyepoxides
US4868230A (en) Cationic, advanced epoxy resins from (1) diglycidyl ethers of phenols (2) diglycidyl ethers of alkane diols and (3) a dihydric phenol
JPH0689274B2 (ja) スルファミン酸およびその誘導体を使用して改良されたカチオン電着組成物
JPH0345091B2 (enrdf_load_stackoverflow)
US4098744A (en) Curable water-borne epoxy resin coating compositions
KR900001373B1 (ko) 캔 코팅용 에폭시 수지의 제조방법
CA2621791A1 (en) Production of stable water dispersion epoxy phosphate ester resins and their aqueous coating compositions
CA1135897A (en) Carboxylated amide polymers and coating compositions containing same
US4482673A (en) Aqueous coating composition comprising self-emulsifiable ester of epoxy and acid containing addition polymer and method of its preparation
JPS6123952B2 (enrdf_load_stackoverflow)
EP0469491B1 (en) Low temperature curable anionic electrodepositable compositions
US4396732A (en) Water soluble amine resins which are Mannich bases
JP3355765B2 (ja) 水性塗料組成物
AU658710B2 (en) Epoxy phosphate ester resin, its production and coating composition containing the resin
JPS5991163A (ja) 第４級アンモニウム基含有物質
JPS601265A (ja) 硬化性カチオン被覆組成物
US5260355A (en) Aqueous dispersion of cationic advanced diglycidyl ether blend
US4387197A (en) Production of water soluble amine resins
US5064880A (en) Cationic diphenol advanced epoxy resins with diglycidylether of aliphatic diol

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19861108

17Q First examination report despatched

Effective date: 19871019

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 3568277

Country of ref document: DE

Date of ref document: 19890323

ET Fr: translation filed
ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

NLS Nl: assignments of ep-patents

Owner name: THE VALSPAR CORPORATION TE MINNEAPOLIS, MINNESOTA,

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980921

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19981005

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990917

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990920

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990921

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991031

BERE Be: lapsed

Owner name: THE VALSPAR CORP.

Effective date: 19991031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20001012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010629

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20010501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST